Dynamics of Organometallic Reaction Mechanisms

在化学系化学结构、动力学和机理B项目的支持下，杨百翰大学化学和生物化学系的Daniel Ess教授正在开发新的基础理论，即在复杂的有机金属反应中，原子在分子内的运动如何决定机理和选择性。这项研究的目的是结合能量和力的量子力学方法、经典的力学运动方程和复杂的溶剂处理来发现有机金属反应的新的反应途径和机理。这项研究可以显著改变对有机金属反应的基本理解、解释和设计，有机金属反应是最重要的化学反应类别之一。该项目结合了计算化学、无机化学、有机化学和计算机科学，是为科学工作者培养本科生和研究生的多样化培训基地。该项目使用准经典直接密度泛函理论和分子动力学轨迹来发现有机金属反应机理和选择性的新基本原理，这是化学中最重要的反应课程之一。这项工作主要关注具有紧密电子自旋态的有机金属反应，以及在轨道上可能发生的自旋交叉。此外，这项工作侧重于开发和应用复杂的协议来模拟有机金属反应轨迹中的显式溶剂。正在研究的有机金属反应包括自由基环化反应、键活化反应和金属氧代反应。这一奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

With support of the Chemical Structure, Dynamics & Mechanisms B Program of the Chemistry Division, Professor Daniel Ess of the Department of Chemistry and Biochemistry at Brigham Young University is developing new foundational theories about how the motion of atoms within molecules determines the mechanisms and selectivity during complex organometallic reactions. The goal of this research is to combine quantum mechanical methods for energy and forces, classical mechanical equations of motion, and sophisticated treatment of solvent to discover new reaction pathways and mechanisms for organometallic reactions. This research could significantly alter the fundamental understanding, interpretation, and design of organometallic reactions, one of the most important classes of chemical reactions. This project combines computational chemistry, inorganic chemistry, organic chemistry, and computer science, and is a diverse training ground to prepare undergraduate and graduate students for the scientific workforce.This project uses quasiclassical direct density functional theory, molecular dynamics trajectories to discover new fundamental principles of mechanisms and selectivity for organometallic reactions, which are one of the most important reaction classes in chemistry. This work focuses on organometallic reactions with close electronic spin states and possible spin crossover during trajectories. Additionally, this work focuses on developing and applying sophisticated protocols for modeling explicit solvent during organometallic reaction trajectories. Organometallic reactions that are being examined include radical cyclization reactions, bond activation reactions, and metal oxo reactions.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.